WO2020067097A1 - Élément de conversion photoélectrique, cellule solaire, procédé de production d'élément de conversion photoélectrique, et procédé de production de cellule solaire - Google Patents

Élément de conversion photoélectrique, cellule solaire, procédé de production d'élément de conversion photoélectrique, et procédé de production de cellule solaire Download PDF

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WO2020067097A1
WO2020067097A1 PCT/JP2019/037470 JP2019037470W WO2020067097A1 WO 2020067097 A1 WO2020067097 A1 WO 2020067097A1 JP 2019037470 W JP2019037470 W JP 2019037470W WO 2020067097 A1 WO2020067097 A1 WO 2020067097A1
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photoelectric conversion
hole transport
conversion element
ring
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PCT/JP2019/037470
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Japanese (ja)
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清隆 深川
洋史 加賀
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • the present invention relates to a photoelectric conversion element and a solar cell, and a method for manufacturing the photoelectric conversion element and a solar cell.
  • Photoelectric conversion elements are used in various optical sensors, copiers, solar cells, and the like. 2. Description of the Related Art Solar cells are expected to be put into full-scale practical use, as they utilize non-depletable solar energy. Among them, a solar cell using a metal halide as a compound having a perovskite-type crystal structure (hereinafter, sometimes referred to as a perovskite compound) has attracted attention because a relatively high photoelectric conversion efficiency can be achieved.
  • a metal halide as a compound having a perovskite-type crystal structure
  • Patent Document 1 describes a manufacturing method including a step of forming a hole injection layer on an anode formed on a support substrate and a step of forming an active layer on the hole injection layer. .
  • Patent Document 2 describes a manufacturing method in which a hole transport layer having a specific uneven surface on a transparent electrode is formed on a transparent electrode, and then a photoelectric conversion layer is formed.
  • the hole injection layer and the hole transport layer can be formed by using a coating solution containing a specific material for forming each layer and a mixed solvent containing water.
  • An object of the present invention is to provide a photoelectric conversion element that can maintain high photoelectric conversion efficiency while using a perovskite compound as a light absorber, and a method for manufacturing a solar cell using the photoelectric conversion element. Further, the present invention relates to a photoelectric conversion element using a perovskite compound as a light absorber, showing a high photoelectric conversion efficiency, and excellent in moisture resistance and durability, and a solar cell using this photoelectric conversion element. It is an object to provide a battery.
  • the present inventors formed a hole transport layer by coating and drying an aqueous composition containing a combination of particles of a non-conductive binder polymer for a conductive organic material having a hole transport function, It has been found that a sufficient carrier conduction path can be constructed in the obtained hole transport layer and that high hydrophobicity can be imparted. Moreover, when a photosensitive layer containing a perovskite compound is formed on the surface of the hole transport layer thus formed, it is possible to increase the photoelectric conversion efficiency of the obtained photoelectric conversion element and suppress the decrease in the photoelectric conversion efficiency over time. I found it. The present invention has been further studied based on these findings, and has been completed.
  • a method for producing a photoelectric conversion element having a photosensitive layer containing a compound having a perovskite crystal structure as a light absorber on the surface of a hole transport layer A step of coating and drying an aqueous composition containing a conductive organic material having a hole transport function and particles of a non-conductive binder polymer, to form a hole transport layer, Forming a photosensitive layer on the surface of the hole transport layer formed in the above step, A method for manufacturing a photoelectric conversion element.
  • ⁇ 2> The method for producing a photoelectric conversion element according to ⁇ 1>, wherein the conductive organic material includes a polymer having a structure represented by the following formula (S1).
  • Ar 1 and Ar 2 represent an arylene group or a heteroarylene group.
  • R 1 represents a substituent.
  • n1 and n2 are integers of 0 or more. However, n1 + n2 ⁇ 1.
  • n3 is an integer of 3 or more. * Indicates a binding site.
  • ⁇ 3> The method for producing a photoelectric conversion element according to ⁇ 1> or ⁇ 2>, wherein the non-conductive binder polymer includes at least one selected from the group consisting of poly (meth) acrylate, polyester, and polyurethane.
  • Mass ratio of content of conductive organic material to content of non-conductive binder polymer in water-based composition [content of conductive organic material: content of non-conductive binder polymer] Is from 80:20 to 99.5: 0.5, the method for producing a photoelectric conversion element according to any one of ⁇ 1> to ⁇ 3>.
  • the compound having a perovskite crystal structure has a group 1 element or a cationic organic group A of the periodic table, a metal atom M other than a group 1 element of the periodic table, and an anionic atom or an atomic group X.
  • ⁇ 6> A method for manufacturing a solar cell, which includes the method for manufacturing a photoelectric conversion element according to any one of ⁇ 1> to ⁇ 5>.
  • the hole transport layer contains a non-conductive binder polymer including at least one selected from the group consisting of poly (meth) acrylate, polyester, and polyurethane, and a conductive organic material having a hole transport function. Photoelectric conversion element.
  • n1 and n2 are integers of 0 or more. However, n1 + n2 ⁇ 1. n3 is an integer of 3 or more. * Indicates a binding site.
  • the photoelectric conversion element and the solar cell of the present invention use a perovskite compound as a light absorber, exhibit high photoelectric conversion efficiency, and have excellent moisture resistance and durability. Further, the method for manufacturing a photoelectric conversion element and the method for manufacturing a solar cell of the present invention can manufacture a photoelectric conversion element and a solar cell that can maintain high photoelectric conversion efficiency by using the above-described perovskite compound as a light absorber.
  • FIG. 1 is a cross-sectional view schematically showing a preferred embodiment of the photoelectric conversion element of the present invention.
  • each formula a part of the notation of each formula may be described as an exponential formula in order to understand the chemical structure of the compound. Accordingly, in each formula, a partial structure is referred to as a (substituted) group, an ion, an atom, or the like. In the present invention, these are represented by the above formula in addition to the (substituted) group, an ion, an atom, or the like. (Substituent) group or ion, or an element.
  • a compound including a complex and a dye
  • the expression of a compound is used to include the compound itself, its salt, and its ion.
  • a compound that is not specified as substituted or unsubstituted is meant to include a compound having an arbitrary substituent within a range that does not impair the intended effect. This is the same for the substituent and the linking group (hereinafter, referred to as a substituent and the like).
  • each substituent and the like when there are a plurality of substituents and the like represented by a specific symbol, or when a plurality of substituents and the like are simultaneously defined, each substituent and the like may be the same or different from each other unless otherwise specified. Is also good. This holds true for the definition of the number of substituents and the like.
  • a plurality of substituents and the like When a plurality of substituents and the like are close to each other (particularly when they are adjacent to each other), they may be connected to each other to form a ring unless otherwise specified.
  • a ring for example, an alicyclic ring, an aromatic ring, or a hetero ring may be further condensed to form a condensed ring.
  • the numerical range represented by using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.
  • the photoelectric conversion element of the present invention has a perovskite crystal structure on the surface of a hole transport layer containing a non-conductive binder polymer containing at least one selected from the group consisting of poly (meth) acrylate, polyester and polyurethane.
  • a photoelectric conversion element having a photosensitive layer containing a compound having the following as a light absorber Is a photoelectric conversion element having a photosensitive layer containing a compound having the following as a light absorber.
  • the hole transport layer contains a conductive organic material having a hole transport function.
  • the photoelectric conversion element of the present invention having the above-described configuration exhibits high photoelectric conversion efficiency and excellent moisture resistance and durability even when a perovskite compound is used as a light absorber. The reason will be described in the method for manufacturing a photoelectric conversion element of the present invention.
  • the configuration of the photoelectric conversion element of the present invention other than the configuration specified in the present invention is not particularly limited, and a known configuration regarding the photoelectric conversion element and the solar cell can be adopted.
  • Each layer constituting the photoelectric conversion element of the present invention is designed according to the purpose, and may be formed in a single layer or a multilayer (laminated structure), for example.
  • the photoelectric conversion element of the present invention preferably has a configuration in which a transparent electrode layer, a hole transport layer, a photosensitive layer and a counter electrode are provided in this order on a transparent substrate, and a configuration having an electron transport layer between the photosensitive layer and the counter electrode is more preferable. preferable.
  • the substrate and each layer may have another layer interposed therebetween, but the hole transport layer and the photosensitive layer are laminated adjacently, and preferably the photosensitive layer and the electron transport layer are laminated adjacently.
  • the other layer is not particularly limited as long as it is a layer usually used for a photoelectric conversion element, and examples thereof include a porous layer and a blocking layer.
  • Materials and members used for a photoelectric conversion element or a solar cell other than the materials and members specified in the present invention can be prepared by an ordinary method.
  • Patent Documents 1 and 2 can be referred to.
  • materials and members used in the dye-sensitized solar cell can be referred to.
  • Dye-sensitized solar cells are described in, for example, JP-A-2001-291534, US Pat. No. 4,927,721, US Pat. No. 4,684,537, US Pat. No. 5,084,365. Specification, US Pat. No. 5,350,644, US Pat. No. 5,463,057, US Pat. No. 5,525,440, JP-A-7-249790, JP-A-2004 Reference can be made to JP-A-220974 and JP-A-2008-135197.
  • the photoelectric conversion element itself of the present invention can be manufactured by a normal manufacturing method, but is preferably manufactured by a method of manufacturing a photoelectric conversion element of the present invention described later.
  • a photoelectric conversion element 10 shown in FIG. 1 is a system in which the photoelectric conversion element 10 is applied to a battery application that causes an operating unit M (for example, an electric motor) to perform work by an external circuit 6.
  • the photoelectric conversion element 10 has a transparent substrate 11, a transparent electrode layer 12, a hole transport layer 13, a photosensitive layer 14, an electron transport layer 15, and a counter electrode 16 in this order.
  • the hole transport layer 13, the photosensitive layer 14, and the electron transport layer 15 are provided in contact with each other.
  • the system 100 to which the photoelectric conversion element 10 is applied functions as a solar cell as described below. That is, in the photoelectric conversion element 10, light that has passed through the transparent substrate 11 and entered the photosensitive layer 14 excites the light absorber. The excited light absorber has high energy electrons and can emit these electrons. The light absorber that has emitted electrons with high energy becomes an oxidant (cation). The electrons emitted from the light absorber move between the light absorber and the electron transport layer 15 to reach the counter electrode 16. The electrons that have reached the counter electrode 16 work in the external circuit 6 and then return to the photosensitive layer 14 via the transparent electrode layer 12 and the hole transport layer 13. The light absorbing agent is reduced by the electrons returned to the photosensitive layer 14. In the photoelectric conversion element 10, the system 100 functions as a solar cell by repeating such a cycle of the excitation of the light absorber and the electron transfer.
  • the transparent substrate 11 is not particularly limited as long as it can support the photosensitive layer 14 and the like.
  • the transparent substrate 11 may be a glass or plastic substrate.
  • Examples of the transparent substrate 11 formed of plastic include a transparent polymer film described in paragraph No. 0153 of JP-A-2001-291534.
  • the transparent substrate 11 is substantially transparent.
  • substantially transparent means that the transmittance of light (wavelength: 300 to 1200 nm) is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • the thickness of the transparent substrate 11 is not particularly limited, and is appropriately set.
  • the thickness is preferably 0.01 ⁇ m to 10 mm, more preferably 0.1 ⁇ m to 5 mm, and particularly preferably 0.3 ⁇ m to 4 mm.
  • the thickness of each layer can be measured by observing the cross section of the photoelectric conversion element 10 using a scanning electron microscope (SEM) or the like.
  • the transparent electrode layer 12 is formed on the surface of the transparent substrate 11 as a conductive film.
  • the transparent electrode layer 12 is preferably formed by coating a conductive metal oxide.
  • a conductive metal oxide As the metal oxide, tin oxide (TO) is preferable, and fluorine-doped tin oxide such as indium-tin oxide (tin-doped indium oxide; ITO) and fluorine-doped tin oxide (FTO) is particularly preferable.
  • the transparent electrode layer 12 is substantially transparent.
  • the thickness of the transparent electrode layer 12 is not particularly limited, and is, for example, preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m. .
  • the coating amount of the metal oxide of this time, if set in the film thickness is not particularly limited, for example, surface area 1 m 2 per 0.1 ⁇ 100 g of the transparent substrate 11 is preferable.
  • the transparent substrate 11 or the transparent electrode layer 12 may have a light management function on the surface.
  • a light management function on the surface of the transparent substrate 11 or the transparent electrode layer 12, an antireflection film described in JP-A-2003-123859, in which a high-refractive film and a low-refractive-index oxide film are alternately laminated, may be provided.
  • the transparent substrate 11 and the transparent electrode layer 12 preferably have a configuration (also referred to as a conductive support) having a transparent substrate 11 made of glass or plastic and a transparent electrode layer 12 formed on the surface of the transparent substrate 11. More preferably, it is a conductive support in which the above-mentioned metal oxide is applied on the surface of a glass or plastic transparent substrate 11 to form a transparent electrode layer 12.
  • the hole transport layer 13 has a hole transport function of transporting holes generated by charge separation of the excited light absorber to the transparent electrode layer 12 (electrons injected from the transparent electrode layer 12 are oxidized by the light absorber.
  • the layer is not particularly limited as long as the layer has at least a function of transporting (replenishing) the layer.
  • the hole transport layer 13 may have an electron blocking function, a hole extraction function, and the like, in addition to the hole transport function. When having these functions, the hole transport layer 13 is also referred to as, for example, an electron blocking layer or a hole extraction layer.
  • the hole transport layer 13 is provided on the transparent electrode layer 12 as an underlayer of the photosensitive layer 14 described below, and contains a conductive organic material and a nonconductive binder polymer described later.
  • the hole transport layer 13 is preferably a solid layer (solid hole transport layer).
  • the conductive organic material contained in the hole transport layer is a polymer that functions as a hole transport material and has a hole transport function and conductivity, and details thereof will be described later.
  • the non-conductive binder polymer is generally a polymer having no hole transport function and conductivity, and is considered to function as a binder for binding the conductive organic material in at least the hole transport layer 13.
  • this polymer is referred to as a non-conductive binder polymer for the sake of convenience to distinguish it from the conductive organic material, but does not exclude a non-conductive polymer having no binder function. . Therefore, in the present invention, the non-conductive binder polymer is not limited to the name, without being limited to a non-conductive polymer having a binder function, in determining the gist or technical scope of the present invention, The term "binder" is not to be considered as invention-specific matter which restrictively interprets the present invention. Details of the non-conductive binder polymer will be described later.
  • the non-conductive binder polymer is considered to be mixed with the conductive organic material in the hole transport layer 3 to form a dense layer in which the non-conductive binder polymer and the conductive organic material are mixed with each other.
  • the hole transport layer 3 has a particle shape in an aqueous composition to be described later. The hole transport layer 3 impairs the particle shape and is mixed with a conductive organic material. It is considered that the conductive binder polymer and the conductive organic material formed a dense layer mixed with each other. This makes it possible to improve the hydrophobicity of the hole transport layer, which is not sufficient with a conductive organic material alone, by mixing a non-conductive binder polymer with respect to a recent high performance solar cell.
  • forming a dense layer means that at least a conductive organic material in the form of particles is densely arranged to form a layer.
  • the non-conductive binder polymer impairs the particle shape and forms a dense layer means that the non-conductive binder polymer is melted once, for example, and is in close contact with the conductive organic material. It means forming a layer.
  • the dense hole transport layer may have voids in the layer as long as the effects of the present invention are not impaired.
  • the above-mentioned dense hole transport layer can be formed by drying an aqueous composition described later.
  • the content of the conductive organic material and the content of the non-conductive binder polymer in the hole transport layer are the same as the content of each polymer in the solid content of the aqueous composition described below.
  • the hole transport material and the non-conductive binder polymer may be appropriately synthesized according to a known method, for example, a method described in Examples described later, or a commercially available product may be used.
  • the thickness of the hole transport layer 13 is not particularly limited, but is preferably 50 ⁇ m or less, more preferably 1 nm to 10 ⁇ m, further preferably 5 nm to 5 ⁇ m, and particularly preferably 10 nm to 1 ⁇ m.
  • the photosensitive layer 14 is preferably provided on the surface of the hole transport layer 13 using a perovskite compound described later as a light absorber.
  • the light absorber only needs to contain at least one specific perovskite compound described below, and may contain two or more types of perovskite compounds.
  • the photosensitive layer 14 may be a single layer or a laminate of two or more layers. When the photosensitive layer 14 has a laminated structure of two or more layers, layers composed of different light absorbers may be laminated, or an intermediate layer containing a hole transport material may be laminated between the photosensitive layers. You may.
  • the photosensitive layer 14 is preferably provided so that excited electrons flow to the counter electrode 16. At this time, the photosensitive layer 14 may be provided in contact with the entire surface of the hole transport layer 13 or the electron transport 15, or may be provided in contact with a part of the surface.
  • the thickness of the photosensitive layer 14 is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, and particularly preferably 0.3 to 30 ⁇ m.
  • the photosensitive layer 14 includes, as light absorbers, “a Group 1 element or a cationic organic group A”, “a metal atom M other than a Group 1 element in the periodic table”, and “an anionic atom or atomic group X”. And a perovskite compound having: In the perovskite compound, the group 1 element of the periodic table or the cationic organic group A, the metal atom M and the anionic atom or the atomic group X are each a cation (for convenience, sometimes referred to as a cation A), a metal, and a metal in the perovskite-type crystal structure.
  • a cationic organic group refers to an organic group having the property of becoming a cation in a perovskite crystal structure
  • an anionic atom or atomic group is an atom or an atomic group having a property of becoming an anion in a perovskite crystal structure.
  • the cation A is a cation of a Group 1 element of the periodic table or an organic cation comprising a cationic organic group A.
  • the cation A may be one kind of cation or two or more kinds of cations. In the case of two or more cations, two or more cations of the first group element of the periodic table or two or more cations may be used. It may contain a kind of organic cation.
  • the cation A preferably contains an organic cation, and more preferably is an organic cation. When two or more cations are present, the ratio of each cation is not particularly limited.
  • the cation of the first group element of the periodic table is not particularly limited, and examples thereof include cations of lithium, sodium, potassium and cesium, and cesium cation is particularly preferable.
  • the organic cation is not particularly limited as long as it is an organic group cation having the above properties, but is more preferably a cationic organic group organic cation represented by the following formula (1). Equation (1): R 1A -N (R 1a ) 3 +
  • R 1A represents a substituent.
  • the substituent that can be taken as R 1A is not particularly limited as long as it is an organic group, but an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group (aromatic heterocyclic group), an aliphatic hetero ring A group or a group represented by the following formula (2) is preferable. Among them, an alkyl group or a group represented by the following formula (2) is more preferable.
  • R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aromatic heterocycle or an aliphatic heterocyclic group. Among them, a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable.
  • Xa represents NR 1c , an oxygen atom or a sulfur atom.
  • R 1b and R 1c each independently represent a hydrogen atom or a substituent.
  • *** represents a bonding position to the N atom in the formula (1).
  • the organic cation of the cationic organic group A is an ammonium cationic organic group A in which R 1a is a hydrogen atom and R 1A and N (R 1a ) 3 in the above formula (1) are bonded.
  • the organic cation includes a cation having a resonance structure in addition to the organic ammonium cation.
  • X a in group which may be represented by the formula (2) is NH (R 1c is a hydrogen atom), an organic cation, and the group and NH 3 that can be represented by the formula (2) coupling
  • an organic amidinium cation which is one of the resonance structures of the organic ammonium cation is also included.
  • Examples of the organic amidinium cation comprising an amidinium cationic organic group include cations represented by the following formula (A am ).
  • the alkyl group which can be taken as R 1A and R 1a is preferably an alkyl group having 1 to 36 carbon atoms, more preferably an alkyl group having 1 to 18 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. Is particularly preferred. For example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl and the like can be mentioned.
  • the cycloalkyl group that can be taken as R 1A and R 1a is preferably a cycloalkyl group having 3 to 10 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl or cyclohexyl.
  • the alkenyl group that can be taken as R 1A and R 1a is preferably an alkenyl group having 2 to 36 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, and still more preferably an alkenyl group having 2 to 6 carbon atoms.
  • the alkynyl group that can be taken as R 1A and R 1a is preferably an alkynyl group having 2 to 36 carbon atoms, more preferably an alkynyl group having 2 to 18 carbon atoms, and still more preferably an alkynyl group having 2 to 4 carbon atoms.
  • ethynyl, butynyl, hexynyl and the like can be mentioned.
  • the aryl group that can be taken as R 1A and R 1a is preferably an aryl group having 6 to 24 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and examples include phenyl.
  • the aromatic hetero ring that can be taken as R 1A and R 1a is a condensed ring, in addition to a group consisting of only a monocyclic aromatic hetero ring, a monocyclic aromatic hetero ring may have another ring such as an aromatic ring.
  • the number of ring-constituting hetero atoms constituting the aromatic hetero ring may be one or more, and the hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. Further, the number of ring members of the aromatic hetero ring is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • Examples of the 5-membered aromatic hetero ring and the fused hetero ring containing the 5-membered aromatic hetero ring include a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a triazole ring, a furan ring, and a thiophene ring.
  • 6-membered aromatic hetero ring and the condensed hetero ring including the 6-membered aromatic hetero ring include pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, and quinazoline ring. Is mentioned.
  • the aliphatic heterocyclic group which can be taken as R 1A and R 1a is a monocyclic group consisting of only an aliphatic hetero ring and an aliphatic fused hetero ring in which another ring (for example, an aliphatic ring) is fused to the aliphatic hetero ring. And a group consisting of a ring.
  • the number of ring-constituting hetero atoms constituting the aliphatic hetero ring may be one or more, and the hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.
  • the number of ring members of the aliphatic hetero ring is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
  • the number of carbon atoms of the aliphatic heterocycle is preferably 0 to 24, more preferably 1 to 18, further preferably 2 to 10, and particularly preferably 3 to 5.
  • Preferred specific examples of the aliphatic hetero ring include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydrofuran ring, an oxane ring (tetrahydropyran ring), a thiane ring, a piperazine ring, a morpholine ring, a quinuclidine ring, a pyrrolidine ring, and azetidine.
  • X a represents NR 1c , an oxygen atom or a sulfur atom, and NR 1c is preferable.
  • R 1c represents a hydrogen atom or a substituent, and is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aromatic heterocyclic ring or an aliphatic heterocyclic group. More preferred.
  • R 1b represents a hydrogen atom or a substituent, and a hydrogen atom is preferable.
  • R 1b examples include an amino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aromatic heterocyclic ring and an aliphatic heterocyclic group.
  • An alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aromatic heterocyclic ring or an aliphatic heterocyclic group, which each of R 1b and R 1c can take, has the same meaning as each group of the above R 1A and is preferable. Things are the same.
  • the amino group that can be taken as R 1b may be an unsubstituted or substituted amino group, and includes an alkylamino group, an alkenylamino group, an alkynylamino group, a cycloalkylamino group, a cycloalkenylamino group, an arylamino group, and a heterocyclic amino group. .
  • the amino group preferably has 0 to 20 carbon atoms.
  • Examples of the group that can be represented by the formula (2) include a (thio) acyl group, a (thio) carbamoyl group, an imidoyl group, and an amidino group.
  • the (thio) acyl group includes an acyl group and a thioacyl group.
  • the acyl group is preferably an acyl group having a total carbon number of 1 to 7, and examples thereof include formyl, acetyl (CH 3 C (OO) —), propionyl, and hexanoyl.
  • the amidino group as a group that can be represented by the formula (2) has a structure (—C (NHNH) NH 2 ) in which R 1b of the above imidoyl group is an amino group and R 1c is a hydrogen atom.
  • R 1A and R 1a may have is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group (an aromatic heterocyclic ring, an aliphatic Heterocyclic group), alkoxy group, alkylthio group, amino group (alkylamino group, arylamino group, etc.), acyl group, alkylcarbonyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, sulfone Examples include an amide group, a carbamoyl group, a sulfamoyl group, a halogen atom, a cyano group, a hydroxy group, or a carboxy group. Each substituent which R 1A and R 1a may have may be further substituted with a substituent.
  • the metal cation M is not particularly limited as long as it is a cation of a metal atom other than a Group 1 element of the periodic table and a metal atom that can have a perovskite crystal structure.
  • metal atoms include metal atoms such as calcium, strontium, cadmium, copper, nickel, manganese, iron, cobalt, palladium, germanium, tin, lead, ytterbium, europium, indium, titanium, and bismuth.
  • M may be one kind of metal cation or two or more kinds of metal cations.
  • the metal cation M is preferably a divalent cation, preferably a divalent lead cation (Pb 2+ ), a divalent copper cation (Cu 2+ ), a divalent germanium cation (Ge 2+ ), and a divalent cation. It is more preferably at least one selected from the group consisting of tin cations (Sn 2+ ), further preferably Pb 2+ or Sn 2+ , and particularly preferably Pb 2+ . When there are two or more metal cations, the ratio of the metal cations is not particularly limited.
  • the anion X represents an anionic atom or an anion of the atomic group X.
  • the anion is preferably an anion of a halogen atom, or an anion of each atomic group of NCS ⁇ , NCO ⁇ , HO ⁇ , NO 3 ⁇ , CH 3 COO ⁇ or HCOO ⁇ .
  • an anion of a halogen atom is more preferable.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the anion X may be an anion of one kind of anionic atom or atomic group, or may be an anion of two or more kinds of anionic atoms or atomic groups.
  • anion atom or anion of an atomic group an anion of an iodine atom is preferable.
  • an anion of two halogen atoms, particularly an anion of a bromine atom or a chlorine atom and an anion of an iodine atom are preferable.
  • the proportion of two or more anions is not particularly limited.
  • the perovskite compound used in the present invention has a perovskite-type crystal structure having the above constituent ions, and is preferably a perovskite compound represented by the following formula (I).
  • A represents a Group 1 element of the periodic table or a cationic organic group.
  • M represents a metal atom other than a Group 1 element of the periodic table.
  • X represents an anionic atom or an atomic group.
  • a represents 1 or 2
  • the group 1 element of the periodic table or the cationic organic group A forms the cation A having a perovskite crystal structure. Therefore, the group 1 element of the periodic table and the cationic organic group A are not particularly limited as long as they are elements or groups capable of forming the perovskite-type crystal structure as the cation A.
  • the element of the first group of the periodic table or the cationic organic group A is synonymous with the element of the first group of the periodic table or the cationic organic group described for the cation A, and preferred examples are also the same.
  • A may contain a group 1 element of the periodic table and a cationic organic group.
  • the metal atom M is a metal atom forming the metal cation M having a perovskite crystal structure.
  • the metal atom M is not particularly limited as long as it is an atom other than the Group 1 element of the periodic table and can be a metal cation M to form a perovskite crystal structure.
  • the metal atom M has the same meaning as the above-described metal atom described for the metal cation M, and preferred ones are also the same.
  • the anionic atom or atomic group X forms the anion X having a perovskite crystal structure.
  • the anionic atom or atomic group X is not particularly limited as long as it is an atom or atomic group capable of forming the perovskite-type crystal structure as the anion X.
  • the anionic atom or atomic group X has the same meaning as the anionic atom or atomic group described in the above-mentioned anion X, and preferred examples are also the same.
  • the perovskite compound represented by the formula (I) is a perovskite compound represented by the following formula (I-1).
  • the perovskite compound is represented by the following formula (I-2). It is a perovskite compound represented.
  • A represents a Group 1 element of the periodic table or a cationic organic group, and has the same meaning as A in the above formula (I), and preferred examples are also the same.
  • M represents a metal atom other than Group 1 element of the periodic table, and has the same meaning as M in the above formula (I), and preferred ones are also the same.
  • X represents an anionic atom or an atomic group, has the same meaning as X in the above formula (I), and preferred examples are also the same.
  • the perovskite compound used in the present invention may be either the compound represented by the formula (I-1) or the compound represented by the formula (I-2), or a mixture thereof. Therefore, in the present invention, it is sufficient that at least one kind of perovskite compound is present as a light absorber, and it is not necessary to clearly distinguish what kind of compound is strictly based on the composition formula, molecular formula, crystal structure, and the like. .
  • perovskite compounds that can be used in the present invention are shown below, but the present invention is not limited to these.
  • the compound represented by the formula (I-1) and the compound represented by the formula (I-2) are described separately.
  • the compound exemplified as the compound represented by the formula (I-1) may be a compound represented by the formula (I-2) depending on the synthesis conditions and the like.
  • a mixture of the compound represented by -1) and the compound represented by formula (I-2) is obtained.
  • the compound exemplified as the compound represented by the formula (I-2) may be a compound represented by the formula (I-1), and the compound represented by the formula (I-1) And a mixture of the compound represented by the formula (I-2) in some cases.
  • Specific examples of the compound represented by the formula (I-1) include, for example, CH 3 NH 3 PbCl 3 , CH 3 NH 3 PbBr 3 , CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBrI 2 , CH 3 NH 3 PbBr 2 I, CH 3 NH 3 SnBr 3 , CH 3 NH 3 SnI 3 , CH 3 NH 3 GeCl 3 , CH (NHNH) NH 3 PbI 3 , CsSnI 3 , CsGeI 3 , Cs 0.04 FA 0.8 CH 3 NH 3 ) 0.16 PbI 2.84 Br 0.16 .
  • the amount of the light absorbing agent used may be an amount covering at least a part of the surface of the hole transport layer 13 on which light is incident, and is preferably an amount covering the entire surface.
  • the content of the perovskite compound in the light absorber is usually 1 to 100% by mass.
  • the electron transport layer 15 is formed between the photosensitive layer 14 and the counter electrode 16 and adjacent to the photosensitive layer 14.
  • the electron transport layer 15 has at least an electron transport function of transporting electrons generated by charge separation of the excited light absorber to the counter electrode 16.
  • the electron transport layer 15 may have a hole blocking function and an electron extraction function in addition to the electron transport function. When having these functions, the electron transport layer 15 is also referred to as, for example, a hole blocking layer or an electron extraction layer.
  • the electron transport layer 15 is formed of an electron transport material that can exhibit the above functions.
  • the electron transport material is not particularly limited, and may be a material usually used for forming an electron transport layer of a photoelectric conversion element. Among them, an organic material (organic electron transport material) is preferable.
  • the organic electron transporting material include fullerene compounds such as [6,6] -Phenyl-C61-Butyric Acid Methyl Ester (PC 61 BM), perylene compounds such as perylenetetracarboxydiimide (PTCDI), and tetracyanoquinodimethane.
  • Low molecular compounds such as (TCNQ), and high molecular compounds are exemplified.
  • the thickness of the electron transport layer 15 is not particularly limited, but is preferably 0.001 to 10 ⁇ m, more preferably 0.01 to 1 ⁇ m.
  • the counter electrode 16 functions as a negative electrode in the solar cell.
  • the counter electrode 16 is not particularly limited as long as it has conductivity, and can usually have the same configuration as the transparent substrate 11. When the strength is sufficiently maintained, the transparent substrate 11 is not always necessary. In the solar cell of the present invention, it is preferable that sunlight be incident on the transparent substrate 11 side. In this case, it is more preferable that the counter electrode 16 has a property of reflecting light.
  • Examples of the material forming the counter electrode 16 include metals such as platinum, gold, nickel, copper, silver, indium, ruthenium, palladium, rhodium, iridium, osmium, and aluminum, and the conductive metal oxide described in the transparent electrode layer 12. Materials, carbon materials, known conductive polymers, and the like. As the carbon material, any material having conductivity in which carbon atoms are bonded to each other may be used, and examples thereof include fullerene, carbon nanotube, graphite, and graphene.
  • the counter electrode 16 is preferably a thin film of a metal or a conductive metal oxide (including a thin film formed by vapor deposition), or a glass substrate or a plastic substrate having these thin films. As the glass substrate or the plastic substrate, glass having a thin film of gold or platinum, or glass on which platinum is deposited is preferable.
  • the thickness of the counter electrode 16 is not particularly limited, but is preferably 0.01 to 100 ⁇ m, more preferably 0.01 to 10 ⁇ m, and particularly preferably 0.01 to 1 ⁇ m.
  • a porous layer made of an insulator or a conductive material may be provided on the transparent electrode layer 12 (usually between the hole transport layer 13). Further, in order to prevent contact between the transparent electrode layer 12 and the counter electrode 16, a blocking layer, a spacer, a separator, and the like can be provided. Further, a hole blocking layer may be provided between the counter electrode 16 and the hole transport layer 13.
  • the solar cell of the present invention is configured using the photoelectric conversion element of the present invention.
  • a photoelectric conversion element 10 provided with an external circuit 6 can be used as a solar cell.
  • the external circuit 6 connected to the transparent electrode layer 12 and the counter electrode 16 a known circuit can be used without any particular limitation.
  • a plurality of photoelectric conversion elements of the present invention can be connected to form a solar cell.
  • the method for producing a photoelectric conversion element of the present invention is a method for producing a photoelectric conversion element having a photosensitive layer containing a compound having a perovskite crystal structure as a light absorber on the surface of a hole transport layer, comprising: A step of coating and drying an aqueous composition containing a conductive organic material having a function and particles of a non-conductive binder polymer to form a hole transport layer, and on the surface of the hole transport layer (preferably Forming a photosensitive layer directly on the surface).
  • the method for manufacturing a solar cell according to the present invention is a method for manufacturing a solar cell through the method for manufacturing a photoelectric conversion element according to the present invention.
  • the step of forming the hole transport layer and the step of forming the photosensitive layer are performed in this order. In other words, it is sufficient that a photosensitive layer can be formed on the surface of the formed hole transport layer, and another step (recycle of the hole transport layer) is performed between the step of forming the hole transport layer and the step of forming the photosensitive layer. (Heating step, storage step, etc.).
  • the step of forming each layer of the photoelectric conversion element may be performed continuously, or may be performed through other steps (discontinuously).
  • the method and conditions for forming each layer other than the step of forming the hole transport layer can be manufactured according to known methods and conditions, for example, methods and conditions described in Patent Documents 1 and 2.
  • the present invention is not limited thereto.
  • ⁇ Formation of transparent substrate and transparent electrode> In the manufacturing method of the present invention, first, the above-mentioned transparent substrate is prepared. Next, the transparent electrode layer 12 is formed on the surface of the prepared transparent substrate 11 according to the method described in the above ⁇ Transparent electrode layer 12> or a known method. In the production method of the present invention, a porous layer or the like can be provided on the surface of the transparent electrode layer 12 if desired.
  • a hole transport layer is formed before forming the photosensitive layer (as a base layer of the photosensitive layer).
  • the hole transport layer is formed by applying and drying an aqueous composition containing a conductive organic material and particles of a non-conductive binder polymer. Thereby, the above-described hole transport layer 13 can be formed.
  • the aqueous composition described below is usually applied to a substrate, preferably to the surface of a transparent electrode layer.
  • the method for applying the aqueous composition is not particularly limited, and a coating method described below can be applied.
  • the application conditions are not particularly limited, and include, for example, the following conditions.
  • the spin-coating may be performed, for example, at a rotation speed of 100 to 10,000 rpm and an application time of 0.1 to 3600 seconds.
  • the atmosphere at the time of coating is not particularly limited, but is preferably a low humidity environment, for example, in dry air or in an inert gas (for example, in an argon gas, a helium gas, or a nitrogen gas).
  • the application temperature can be set as appropriate, for example, 10 to 40 ° C.
  • the application amount of the aqueous composition is determined so as to be the thickness of the hole transport layer to be formed.
  • the aqueous composition is applied to the surface of the substrate, preferably the surface of the transparent electrode layer.
  • the applied aqueous composition is dried.
  • the method of drying is not particularly limited, and includes drying without heating, heating and drying, and heating and drying are preferred.
  • the drying temperature (under normal pressure) is not particularly limited.
  • the lower limit of the drying temperature is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, and even more preferably the glass transition temperature or the melting point or higher of the nonconductive binder polymer.
  • the drying of the aqueous composition is performed at a temperature equal to or higher than the glass transition temperature or the melting point of the non-conductive binder polymer, the particles of the non-conductive binder polymer are melted to form a highly hydrophobic dense hole transport layer. Can be formed.
  • the drying temperature does not have to be set low in order to suppress the decomposition of the perovskite compound due to a slight amount of remaining moisture.
  • the drying temperature is preferably 300 ° C. or lower, more preferably 200 ° C. or lower, and even more preferably 150 ° C. or lower.
  • Drying conditions other than the drying temperature are not particularly limited.
  • the drying time cannot be unambiguously determined according to the drying temperature or the like, but is set to a time during which the aqueous solvent can be removed, for example, 1 minute to 10 hours.
  • the atmosphere at the time of drying is not particularly limited, but an atmosphere under the above-described application conditions is preferable.
  • a hole transport layer can be formed.
  • the resulting hole transport layer is dense and highly hydrophobic, and a carrier conduction path is built.
  • the details of the reason are not yet clear, but are considered as follows. That is, when the aqueous composition containing the conductive organic material and the particles of the non-conductive binder polymer was applied and dried as described above, water in the aqueous composition was effectively removed (the amount of residual water was reduced). A (reduced) hole transport layer can be formed. This is presumably because the non-conductive binder polymer is contained in the aqueous composition as particles, so that it is difficult to include water inside the particles, and water can be effectively and quickly evaporated and removed during drying.
  • the conductive organic material contained in the system has relatively high hydrophilicity, and the affinity between the conductive organic material and the aqueous solvent is increased due to the coexistence of non-conductive binder polymer particles. It will be even higher. In this way, it is considered that the function and function of the conductive organic material are effectively exhibited, and the carrier conduction path is easily formed appropriately.
  • a non-conductive binder polymer is mixed into the hole transport layer, it is considered that the carrier conductivity is deteriorated.
  • the carrier conductivity is not impaired, which is specific to the present invention. It has an effect.
  • the particle shape of the non-conductive binder polymer is broken to form a dense hole transport layer in which the conductive organic material and the non-conductive binder polymer are mixed with each other. It can be considered that a more preferable carrier conduction path can be constructed because it can be formed. In this way, a hole transporting layer having high density due to high density due to low residual water content can be formed. Therefore, the photoelectric conversion device of the present invention including the hole transport layer and the photosensitive layer provided on the surface thereof exhibits high photoelectric conversion efficiency. Moreover, it is possible to effectively block water in the hole transport layer or outside from entering the photosensitive layer via the interface with the hole transport layer, and to maintain high photoelectric conversion efficiency even in a high humidity environment (excellent). Exhibiting high moisture resistance and durability).
  • the aqueous composition is an aqueous dispersion containing a conductive organic material having a hole transport function, and particles of a non-conductive binder polymer, and contains other components as long as the effects of the present invention are not impaired. It may be.
  • aqueous dispersion means that a compound that is not water-soluble (a water-insoluble compound) does not form a precipitate (even after standing for 12 hours) in an aqueous dispersion medium at 25 ° C. (does not settle).
  • a liquid in a state specifically, a liquid in which a water-insoluble compound is forming micelle particles in an aqueous dispersion medium, a state in which the water-insoluble compound is uniformly dispersed in an aqueous dispersion medium, and the like. It includes certain liquids (dispersions, latex) and the like.
  • a dispersion in which at least a non-conductive binder polymer described below is in the form of particles and is present in an aqueous dispersion medium is preferable.
  • the conductive organic material may be dissolved in the aqueous dispersion medium, but is preferably dispersed in the form of particles.
  • water-soluble refers to the property of being soluble in water at a certain concentration or more, and specifically, the property of being soluble in water at 25 ° C. in an amount of 5 g or more is preferable.
  • the conductive organic material has conductivity, and preferably has a hole transport function.
  • the conductive organic material is preferably an organic compound, and more preferably a polymer.
  • having conductivity means that when incorporated in a hole transport layer of a photoelectric conversion element, the conductive organic material exhibits a property of transporting injected electrons, and a conductive organic material includes a conductor and a semiconductor.
  • the hole transport function is a function obtained by the arrangement of the energy level of the highest occupied orbital (HOMO) of the conductive organic material and the valence band level of the perovskite compound (the level of the energy level).
  • the conductive organic material having the hole transporting function means that the light absorbing agent excited when the conductive organic material is incorporated into the hole transporting layer of the photoelectric conversion element (when the hole transporting layer is formed). Indicates that it can transport holes generated by charge separation to the transparent electrode layer 12.
  • the polymer having conductivity means that electrons injected from the transparent electrode layer 12 can be transported to the photosensitive layer 14 when the polymer is incorporated in the hole transport layer of the photoelectric conversion element (semi-conductive property).
  • the conductive organic material preferably exhibits water insolubility (a water-insoluble compound), and more preferably is dispersed as particles in an aqueous dispersion medium (aqueous composition).
  • the conductive organic material When the conductive organic material is dispersed as particles, the amount of water remaining in the hole transport layer can be effectively reduced, and the hydrophobicity can be further improved.
  • the average particle size of the particles is not particularly limited and can be set as appropriate.
  • the thickness is preferably 1 nm to 10 ⁇ m, and more preferably 10 to 1000 nm.
  • the average particle size of the conductive organic material can be measured in the same manner as the non-conductive binder polymer.
  • a conductive organic material a known compound, for example, a hole transport material used for a hole transport layer of a photoelectric conversion element can be used without any particular limitation.
  • organic hole transport materials described in paragraphs 0209 to 0212 of JP-A-2001-291534 can be used.
  • the organic hole transporting material is preferably a conductive polymer such as a polythiophene polymer, a polyaniline polymer, a polypyrrole polymer, a polysilane polymer, a poly (triarylamine) polymer, and two rings.
  • Is a spiro compound sharing a central atom having a tetrahedral structure such as C, Si, an aromatic amine compound having a triarylamino group, a triphenylene compound, a nitrogen-containing heterocyclic compound, a porphyrin, a phthalocyanine, a cyclic compound such as a naphthalocyanine, Liquid crystal cyano compounds and the like can be mentioned.
  • hole transport materials described in WO 2015/107454, WO 2015/114521, or WO 2014/111365 may be mentioned.
  • the conductive organic material may contain one kind of the above-described hole transporting materials alone or two or more kinds thereof, and preferably contains a polymer having a structure represented by the following formula (S1), A hole transport layer other than the polymer (for example, the above-described hole transport material) may be included.
  • the content of the polymer having the structure represented by the formula (S1) in the conductive organic material is not particularly limited, and is preferably, for example, 10 to 100% by mass.
  • the following formula (S1) can be formed in that a dense network of polymers can be formed in the hole transport layer to contribute to building a sufficient carrier conduction path and improving the hydrophobicity of the hole transport layer. It is preferable to include a polymer having a structure represented by ()).
  • Ar 1 and Ar 2 represent an arylene group or a heteroarylene group.
  • R 1 represents a substituent.
  • n1 and n2 are integers of 0 or more. However, n1 + n2 ⁇ 1.
  • n3 is an integer of 3 or more. * Indicates a binding site with, for example, a terminal structure described below.
  • Ar 1 and Ar 2 are an arylene group or a heteroarylene group, respectively, and an arylene group is preferable.
  • the arylene group that can be taken as Ar 1 and Ar 2 may be a single ring or a condensed ring, and is preferably a single ring.
  • the number of condensed rings is not particularly limited, and is preferably 2 to 5, more preferably 2 or 3, and more preferably 2. More preferred.
  • Examples of the monocyclic arylene group include a group comprising a benzene ring (phenylene group).
  • Examples of the condensed arylene group include a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a chrysene ring, a picene ring, and a pyrene ring.
  • a phenylene group or a group comprising a naphthalene ring or a fluorene ring is preferable.
  • the number of ring-constituting atoms of the arylene group that can be taken as Ar 1 and Ar 2 is not particularly limited, but is preferably 6 to 30, more preferably 6 to 15, and still more preferably 6 to 13.
  • the heteroarylene group that can be taken as Ar 1 and Ar 2 may be a single ring or a condensed ring, and is preferably a single ring.
  • the monocyclic heteroarylene group is not particularly limited, but includes a carbon atom and at least one (preferably one or two) heteroatoms (for example, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, a selenium atom) Or a phosphorus atom) as a ring-constituting atom.
  • the monocyclic heteroarylene group is not particularly limited, but is preferably a 5- or 6-membered ring group.
  • thiophene ring furan ring, pyrrole ring, selenophene ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, imidazole ring, pyrazole ring, thiadiazole ring, oxadiazole ring, triazole ring, silole ring, phosphole ring , A pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring or a tetrazine ring, in which two hydrogen atoms have been removed from each ring.
  • the ring constituting the condensed heteroarylene group includes a ring formed by condensing a plurality of monocyclic heteroaryl rings and a ring formed by condensing a plurality of monocyclic heteroaryl rings and a plurality of monocyclic hydrocarbon rings. Is mentioned.
  • the number of condensed rings is not particularly limited, but is preferably 2 to 5, more preferably 2 or 3, and even more preferably 2.
  • Examples of the condensed heteroarylene group include a benzofuran ring, isobenzofuran ring, benzothiophene ring, benzoisothiophene ring, indazole ring, indole ring, isoindole ring, indolizine ring, carbazole ring (dibenzopyrrole ring), and quinoline Ring, isoquinoline ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, benzoisothiazole ring, benzimidazole ring, benzotriazole ring, dibenzofuran ring, dibenzothiophene ring, thienopyridine ring, silafluorene ring (dibenzosilole ring), Thienothiophene ring, trithiophene ring, cyclopentadithiophene ring, cyclopentadifuran ring, be
  • the number of ring-constituting carbon atoms of the heteroaryl group that can be taken as Ar 1 and Ar 2 is not particularly limited, but is preferably 0 to 24, and more preferably 1 to 18.
  • Ar 1 and Ar 2 are each preferably an arylene group, more preferably a phenylene group.
  • the aryl group and heteroaryl group that can be taken as Ar 1 and Ar 2 may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a substituent that R 1 described below may have.
  • the number of substituents of Ar 1 and Ar 2 is not particularly limited, and is appropriately determined. Adjacent substituents may combine with each other to form a ring. In the case where adjacent Ar 1 s , adjacent Ar 2 s , and further Ar 1 and Ar 2 bonded to the nitrogen atom in the formula (S1) each have a substituent, these substituents are bonded to each other to form a ring. May be formed.
  • the condensed ring formed is interpreted as a condensed ring arylene group or heteroarylene group as a whole.
  • Ar 1 and Ar 2 may be the same or different, but are preferably the same.
  • n1 and n2 are each an integer of 0 or more, preferably 1 or more.
  • the upper limit is not particularly limited, but is preferably an integer of 10 or less, more preferably an integer of 5 or less.
  • n1 and n2 are more preferably 1 or 2, respectively.
  • n1 and n2 may be the same or different.
  • n1 and n2 are an integer of 1 or more in total (n1 + n2 ⁇ 1), preferably an integer of 1 to 20 in total, and more preferably an integer of 2 to 10 in total. If n1 and n2 is an integer of 2 or more, two or more Ar 1 and Ar 2 each may be the same or different.
  • R 1 represents a substituent.
  • the substituent that can be taken as R 1 is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aliphatic heterocyclic group. Among them, an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group are preferable.
  • the aryl group and the heteroaryl group that can be taken as R 1 have the same meanings as the aryl group and the heteroaryl group that can be taken as the above Ar 1 , respectively.
  • the substituent which can be taken as R 1 may further have a substituent.
  • substituents that may be further included are not particularly limited, and include, for example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group (an aromatic heterocyclic group and an aliphatic heterocyclic group).
  • R 1 Alkoxy group, alkylthio group, amino group (alkylamino group, arylamino group, etc.), acyl group, alkylcarbonyloxy group, alkenylcarbonyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, sulfone Examples include an amide group, a carbamoyl group, a sulfamoyl group, a halogen atom, a cyano group, a hydroxy, a carboxy group, and a silyl group (such as an alkylsilyl group and an arylsilyl group).
  • the number of substituents that the substituent that can be taken as R 1 may further have is not particularly limited and is appropriately determined, and includes, for example, 1 to 7.
  • n3 is an integer of 3 or more, preferably an integer of 3 to 5000, more preferably an integer of 3 to 1000, further preferably an integer of 5 to 200, and particularly preferably an integer of 5 to 50.
  • n3 is the number of repeating units to which the repeating units enclosed in square brackets in the above formula (S1) are linked, and three or more repeating units may be the same or different.
  • the polymer having the structure represented by the formula (S1) may include at least one polymer in which n3 is an integer of 3 or more, and may be a mixture of polymers having a plurality of different n3 from each other. Good.
  • the polymer having the structure represented by the formula (S1) has the structure represented by the formula (S1) as a partial structure of the polymer, and is incorporated as a part of the main chain.
  • the main chain of the polymer refers to a linear molecular chain in which all other molecular chains constituting the polymer can be regarded as pendant to the main chain.
  • the functional group of the terminal of the polymer is not included in the main chain.
  • the terminal structure is not particularly limited, and is uniquely determined by the type of the substrate used in the synthesis, the type of the quenching agent (reaction terminator) in the synthesis, and the like. Not determined.
  • the terminal structure include a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group, an aryl group, and a heteroaryl group.
  • the weight average molecular weight of the polymer having the structure represented by the above formula (S1) preferably satisfies the weight average molecular weight of the conductive organic material described later, and the polymer network is formed more densely, From the viewpoint that the conversion efficiency can be further improved, it is more preferably from 500 to 1,000,000, and still more preferably from 1,000 to 50,000.
  • the polymer having the structure represented by the above formula (S1) can be synthesized by a known method, or a commercially available product can be used.
  • n has the same meaning as n3 in formula (S1).
  • two of Ar 2-1 to Ar 2-4 are 9,9-dimethyl-fluorene-2,7-diyl groups and the other two are phenyl groups, and these bonds are combined. The order is not particularly limited.
  • the weight average molecular weight is not particularly limited, but is preferably, for example, 500 to 2,000,000, and more preferably 1,000 to 100,000.
  • the method for measuring the weight average molecular weight means a value measured by gel permeation chromatography (GPC) unless otherwise specified.
  • the measurement apparatus and measurement conditions are basically based on the following conditions. Depending on the type of the polymer, an appropriate carrier (eluent) and a column suitable for the carrier may be selected and used. For other items, refer to JIS K 7252-1 to 4: 2008. In addition, about a hardly soluble polymer, it shall measure at the density
  • the aqueous composition may contain one kind of the conductive organic material alone or two or more kinds.
  • the method of dispersing the conductive organic material in the aqueous composition in a particulate form is not particularly limited, and examples thereof include emulsification methods such as mechanical emulsification and phase inversion emulsification. Among them, a mechanical emulsification method performed in the presence of a surfactant is preferable.
  • the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a betaine surfactant, and an anionic surfactant is preferable from the viewpoint of dispersibility.
  • fluorine (alkyl fluoride) surfactants and silicone surfactants described in JP-A-2003-322926, JP-A-2004-325707, and JP-A-2004-309806 are also included.
  • the non-conductive binder polymer may be any polymer compound that does not exhibit conductivity, and is preferably a polymer compound having the above function as a binder, and more preferably a polymer.
  • “not exhibiting conductivity” refers to a property in which injected electrons cannot be transported when incorporated into a hole transport layer of a photoelectric conversion element.
  • the non-conductive binder polymer is considered to exhibit a function as a binder (a function to bind and adhere a conductive organic material) at least in the hole transport layer.
  • Examples of such a non-conductive binder polymer include known compounds and ordinary insulating polymers, and preferably include an insulating polymer.
  • the poly (meth) acrylate includes a polymer containing a component derived from (meth) acrylic acid, and a copolymer containing a component derived from a compound having an ethylenically unsaturated group.
  • the compound having an ethylenically unsaturated group is not particularly limited as long as it is a compound copolymerizable with (meth) acrylate, and examples thereof include a styrene compound, a (meth) acrylonitrile compound, and a (meth) acrylamide compound.
  • the content of the copolymer component in the poly (meth) acrylate is appropriately set, and may be, for example, less than 50 mol%.
  • the non-conductive binder polymer is at least selected from the group consisting of polyester, polyurethane, and poly (meth) acrylate in terms of preparation of the aqueous dispersion, and further, in terms of photoelectric conversion efficiency and humidity resistance of the photoelectric conversion element. It is preferable to include one kind.
  • the non-conductive binder polymer preferably has a glass transition temperature or melting point of 150 ° C. or lower, more preferably 100 ° C. or lower.
  • the non-conductive binder polymer in the drying step described below, the non-conductive binder polymer is melted to form a highly hydrophobic dense hole transport layer. can do.
  • the glass transition temperature or the melting point of the non-conductive binder polymer can be measured by differential scanning calorimetry (DSC). A specific measuring method is performed according to the method described in JIS K 7121 (1987) or JIS K 6240 (2011). The method for measuring the glass transition temperature will be described more specifically. When the glass transition temperature (Tg) is determined, the temperature is maintained at about 50 ° C.
  • the glass transition temperature in this specification is defined as a straight line obtained by extending the low-temperature-side baseline in the DTA curve or DSC curve to the high-temperature side, and a tangent drawn at a point where the gradient of the curve of the stepwise change portion of the glass transition becomes maximum. As the temperature at the intersection of
  • the mass average molecular weight of the non-conductive binder polymer is not particularly limited, but is preferably, for example, 500 to 2,000,000, and more preferably 1,000 to 300,000.
  • the mass average molecular weight can be measured in the same manner as the conductive organic material.
  • This non-conductive binder polymer is a water-insoluble compound exhibiting water-insolubility, and is dispersed as particles in an aqueous dispersion medium (aqueous composition).
  • the method of dispersing the non-conductive binder polymer in the form of particles in the aqueous composition is not particularly limited, and examples thereof include mechanical emulsification, emulsification methods such as phase inversion emulsification, and methods of dispersing simultaneously with polymerization by emulsion polymerization. .
  • a method of dispersing by a mechanical emulsification method and a method of dispersing by an emulsion polymerization are preferable.
  • the average particle size of the non-conductive binder polymer particles in the aqueous composition is not particularly limited and can be set as appropriate.
  • the average particle size of the non-conductive binder polymer is 1 nm because the non-conductive binder polymer can be quickly melted to form a dense hole transport layer having high hydrophobicity. It is preferably from 10 to 10 ⁇ m, more preferably from 1 to 500 nm.
  • the average particle size of the non-conductive binder polymer is preferably a volume average particle size, and can be measured by a laser diffraction / scattering type particle size distribution meter.
  • the measuring device examples include a particle size distribution measuring device “Microtrack MT-3300II” (manufactured by Nikkiso Co., Ltd.).
  • the aqueous composition contains one kind of the nonconductive binder polymer alone or contains two or more kinds. You may.
  • the aqueous dispersion medium contains at least water and, if necessary, at least one organic solvent. It is preferable to contain an organic solvent from the viewpoint of applicability.
  • the water is not particularly limited, but water containing no impurities such as ion-exchanged water and distilled water is preferably used.
  • the organic solvent is not particularly limited, and examples thereof include a water-soluble organic solvent and a water-insoluble organic solvent. Examples of the water-soluble organic solvent include an alkyl alcohol solvent having 1 to 4 carbon atoms, an alkane polyol solvent, a sugar alcohol solvent, and a glycol ether solvent.
  • water-insoluble organic solvent examples include an alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, a lactone solvent, a halogen solvent, and a sulfide solvent, which will be described later.
  • the aqueous composition may contain one type of organic solvent alone or two or more types of organic solvents.
  • the aqueous composition may contain other components other than those described above, for example, a hole transport material dopant, a surfactant, and the like.
  • the content of the conductive organic material in the aqueous composition is appropriately set, but is preferably 70 to 99.7% by mass in terms of photoelectric conversion efficiency and moisture resistance / durability in 100% by mass of solid content. Preferably, from 80 to 99.5% by mass, more preferably from 90 to 99% by mass, from the viewpoint that the photoelectric conversion efficiency can be further improved without impairing the moisture resistance and durability.
  • the content of the non-conductive binder polymer in the aqueous composition is appropriately set, but is from 0.3 to 30% by mass in terms of photoelectric conversion efficiency and moisture resistance durability in 100% by mass of solid content.
  • the aqueous composition contains the above-mentioned other components
  • the content of the other components in the aqueous composition is not particularly limited, and for example, is preferably 3% by mass or less.
  • the content of each component is set as the solid content in the aqueous composition so that the conductive organic material, the non-conductive binder polymer, and the other components are 100% by mass in total. Is determined within the range.
  • the solid content refers to a component which does not disappear by volatilization or evaporation when the aqueous composition is dried at 170 ° C. for 6 hours in a nitrogen atmosphere at a pressure of 1 mmHg. Typically, it refers to components other than the aqueous dispersion medium.
  • the mass ratio of the content of the conductive organic material to the content of the non-conductive binder polymer is particularly Although not limited, it is preferably 80:20 to 99.5: 0.5, and more preferably 90:10 to 99: 1, in terms of photoelectric conversion efficiency and moisture resistance and durability.
  • the content of the aqueous dispersion medium in the aqueous composition is not particularly limited as long as the non-conductive binder polymer can be dispersed as particles, and is preferably, for example, 30 to 99.9% by mass, and 40 to 99.9 mass%. The content is more preferably 99.5% by mass, and even more preferably 50 to 99% by mass.
  • the content of the aqueous dispersion medium indicates the total content of the water content and the organic solvent content.
  • the content of the organic solvent in the aqueous dispersion medium is not particularly limited as long as the non-conductive binder polymer can be dispersed as particles, and is, for example, 0.01 to 50% by mass in 100% by mass of the aqueous dispersion medium. It is preferably 0.05 to 20% by mass, and more preferably 0.1 to 10% by mass.
  • the content of the other components is appropriately set within a range that does not impair the effects of the present invention.
  • the preparation method is not particularly limited as long as at least the non-conductive binder polymer can be dispersed in particles, and a known dispersion liquid preparation method, for example, an emulsification method can be applied. Specifically, a method of adding a solution in which a conductive organic material and a non-conductive binder polymer are dissolved in an organic solvent and water in the presence of a surfactant (dispersant, emulsifier), etc .; To prepare a dispersion of a non-conductive binder polymer by emulsion polymerization or the like, and mixing the dispersion with a conductive organic material, preferably a dispersion of a conductive organic material.
  • a surfactant dispersant, emulsifier
  • the photosensitive layer 14 is provided on the surface of the hole transport layer 13.
  • the perovskite compound used for forming the photosensitive layer can be synthesized from a compound represented by the following formula (II) and a compound represented by the following formula (III).
  • A represents a Group 1 element of the periodic table or a cationic organic group, and has the same meaning as A in the above formula (I), and preferred examples are also the same.
  • X represents an anionic atom or an atomic group, and has the same meaning as X in the above formula (I), and preferred examples are also the same.
  • M represents a metal atom other than the Group 1 element of the periodic table, and has the same meaning as M in the above formula (I), and preferred examples are also the same.
  • X represents an anionic atom or an atomic group, and has the same meaning as X in the above formula (I), and preferred examples are also the same.
  • a method for providing the photosensitive layer 14 includes a wet method and a dry method, and is not particularly limited.
  • a wet method is preferable, and for example, a method of contacting with a light absorber composition (solution) containing an absorber is preferable.
  • a light absorber composition for forming the photosensitive layer 14 is prepared.
  • the light absorber composition may be a composition containing the perovskite compound itself. preferable.
  • the molar ratio between the compound (AX) represented by the formula (II) and the compound (MX 2 ) represented by the formula (III) is appropriately adjusted according to the purpose. .
  • the molar ratio of AX and MX 2 is 1: 1 to 10: 1.
  • the light absorbent composition preferably after mixing the AX and MX 2 at a predetermined molar ratio by heating can be prepared.
  • the composition is usually a solution, but may be a suspension.
  • the heating conditions are not particularly limited, but the heating temperature is preferably 30 to 200 ° C, more preferably 60 to 150 ° C.
  • the heating time is preferably 0.5 to 100 hours, more preferably 1 to 20 hours, and still more preferably 1 to 3 hours.
  • the solvent or dispersion medium described below can be used.
  • the prepared light absorbent composition is brought into contact with the surface of the hole transport layer 13. Specifically, it is preferable to apply the light absorber composition on the surface of the hole transport layer 13 or to immerse the hole transport layer 13 in the light absorber composition. As a result, the perovskite compound is deposited or adsorbed on the surface of the hole transport layer 13 to form a photosensitive layer.
  • the contact temperature is preferably 5 to 100 ° C.
  • the immersion time is preferably 5 seconds to 24 hours, more preferably 20 seconds to 1 hour.
  • the conditions for coating can be appropriately determined according to the film thickness and the like.
  • drying of the light absorber composition is preferably performed by heat, and is usually performed by heating to 20 to 300 ° C., preferably 50 to 170 ° C.
  • the AX-containing AX composition (ammonium salt composition) and the MX 2 -containing MX 2 composition (metal salt composition) are separately brought into contact with the surface of the hole transport layer 13. There are also methods. In this method, it may be contacted previously with any composition, but preferably is contacted with MX 2 composition above. The molar ratio of AX and MX 2 put to this method, a method of contacting and conditions, further drying conditions are the same as the above method. In this method, instead of the contact of the AX composition and the MX 2 composition, the AX or MX 2, can also be deposited.
  • a dry method such as vacuum deposition using a compound or a mixture from which the solvent of the above-mentioned light absorber composition has been removed can be mentioned.
  • the AX and the MX 2 simultaneously or sequentially, and a method of depositing.
  • a photosensitive layer can be formed according to a method for synthesizing a perovskite compound.
  • a method for synthesizing a perovskite compound for example, the methods described in Patent Documents 1 and 2 can be referred to. Also, J.I. Am. Chem. Soc. , 2009, 131 (17), p. The method described in 6050-6051 can also be referred to.
  • the photosensitive layer 14 directly laminated on the surface of the hole transport layer 13 is formed.
  • the electron transport layer 15 is formed on the photosensitive layer 14.
  • the electron transport layer 15 can be formed, for example, by applying and drying an electron transport material composition containing an electron transport material.
  • the application temperature and application time are not particularly limited, and are appropriately set.
  • the drying conditions of the electron transporting material composition are preferably heating conditions, and generally heating conditions of 30 to 200 ° C., preferably 40 to 110 ° C. can be applied.
  • the counter electrode 16 is further formed on the electron transport layer 15.
  • the counter electrode 16 can be formed by a known method.
  • the photoelectric conversion element of the present invention can be manufactured.
  • each layer can be set by appropriately changing the concentration of the composition (solution or dispersion) forming each layer and the number of times of application (immersion time).
  • Each composition may contain additives such as a dispersing aid and a surfactant, if necessary.
  • Examples of the solvent or dispersion medium used in the method for manufacturing a photoelectric conversion element include, but are not particularly limited to, the solvents described in JP-A-2001-291534.
  • an organic solvent is preferable, and an alcohol solvent, an amide solvent, a nitrile solvent, a hydrocarbon solvent, a lactone solvent, a halogen solvent, a sulfide solvent, and a mixed solvent of two or more of these are preferable.
  • As the mixed solvent a mixed solvent of an alcohol solvent and a solvent selected from an amide solvent, a nitrile solvent, and a hydrocarbon solvent is preferable.
  • methanol, ethanol, isopropyl alcohol, ⁇ -butyrolactone, n-propyl sulfide, chlorobenzene, acetonitrile, N, N-dimethylformamide (DMF) or dimethylacetamide, or a mixed solvent thereof is preferable.
  • the method of applying the composition for forming each layer is not particularly limited, and includes spin coating, extrusion die coating, blade coating, bar coating, screen printing, stencil printing, roll coating, curtain coating, spray coating, dip coating, inkjet printing, Known coating methods such as immersion can be used. Among them, a spin coating method, a screen printing method, an immersion method and the like are preferable.
  • the photoelectric conversion element of the present invention can be subjected to an efficiency stabilization treatment such as annealing, light soaking, or standing in an oxygen atmosphere, as appropriate.
  • the solar cell of the present invention can be manufactured through the above-described method for manufacturing a photoelectric conversion element of the present invention. Specifically, a solar cell can be manufactured by connecting the external circuit 6 to the transparent electrode layer 12 and the counter electrode 16 to the photoelectric conversion element manufactured as described above. In the method for manufacturing a solar cell according to the present invention, a plurality of photoelectric conversion elements may be connected to form a photoelectric conversion element unit before or after the external circuit 6 is connected, and a solar cell may be formed using the photoelectric conversion element unit.
  • aqueous dispersion (PTAA concentration: 2% by mass) in which conductive polymer particles are dispersed in an aqueous dispersion medium.
  • the average particle size of the conductive polymer particles in the aqueous dispersion was 200 nm.
  • PEDOT / PSS aqueous dispersion Preparation of PEDOT / PSS aqueous dispersion
  • PEDOT / PSS concentration: 2.8 mass% aqueous dispersion, manufactured by Aldrich water was added so that the PEDOT / PSS concentration was 2 mass%, and an aqueous dispersion ( (PEDOT / PSS concentration: 2% by mass).
  • the average particle size of the conductive polymer particles in the aqueous dispersion was 200 nm.
  • the conductive polymer has a weight average molecular weight of 100,000 and has a hole transport function. This conductive polymer had a solubility of less than 0.001 g in 100 g of water at 25 ° C., and was insoluble in water.
  • a Spiro aqueous dispersion in which particles of a conductive low-molecular compound are dispersed in an aqueous dispersion medium (conductive low-molecular compound concentration: 2% by mass).
  • the average particle size of the conductive low molecular weight compound particles in the aqueous dispersion was 520 nm.
  • the conductive low-molecular compound has a hole transporting function and is a water-insoluble compound having a solubility in 100 g of water at 25 ° C. of less than 0.001 g.
  • aqueous dispersion of non-conductive binder polymer Preparation of poly (meth) acrylate aqueous dispersion 13.9 g of Neoperex G-15 (16% by mass aqueous solution, manufactured by Kao Corporation) as an anionic emulsifier and 786 g of water were added to the flask, and heated to 90 ° C. under a nitrogen atmosphere.
  • the numerical value at the lower right of the parenthesis indicates the molar ratio of each component in the poly (meth) acrylate.
  • Poly (meth) acrylate does not have conductivity.
  • the poly (meth) acrylate is a water-insoluble compound having a mass average molecular weight of 10,000, a glass transition temperature of 85 ° C, and a solubility of less than 0.001 g in 100 g of water at 25 ° C.
  • aqueous polyester dispersion As an aqueous polyester dispersion, Eastek 1100 (manufactured by Eastman) was used to add water so that the concentration of the polyester was 2% by mass. The average particle size of the polyester particles in the aqueous polyester dispersion was 50 nm. This polyester is a water-insoluble compound having no conductivity, having a weight average molecular weight of 15,000, a glass transition temperature of 40 ° C., and a solubility of less than 0.001 g in 100 g of water at 25 ° C. Hydran WLI-615 (manufactured by DIC) was used as a polyurethane aqueous dispersion.
  • the average particle size of the polyurethane particles in the aqueous polyurethane dispersion was 300 nm.
  • Polyurethane has no conductivity.
  • this polyurethane is a water-insoluble compound having a mass average molecular weight of 30,000, a glass transition temperature of 30 ° C., and a solubility of less than 0.001 g in 100 g of water at 25 ° C.
  • Table 1 shows the composition of the aqueous composition and the like.
  • the "mass ratio" in Table 1 indicates the mass ratio of the conductive organic material to the non-conductive binder polymer [content of the conductive organic material: content of the non-conductive binder polymer] in the aqueous composition. Show. In each aqueous composition, the content of the aqueous dispersion medium (total amount of water and the organic solvent) is 98.2% by mass, and the content of the organic solvent is 9.8% by mass.
  • the photoelectric conversion device 10 shown in FIG. 1 was manufactured by the following procedure.
  • a fluorine-doped SnO 2 conductive film (transparent electrode layer 12, 300 nm thick) was formed on a glass substrate (transparent substrate 11, 2.2 mm thick) to produce a conductive support.
  • the aqueous dispersion No. 1 was applied on a transparent electrode layer of a conductive support by a spin coating method (at 3,000 rpm for 90 seconds) in a nitrogen gas atmosphere at room temperature.
  • the aqueous dispersion No. 1 was dried at 120 ° C. for 10 minutes in a nitrogen gas atmosphere under normal pressure to form a hole transport layer 13 having a thickness of 50 nm.
  • This hole transport layer was made of the aqueous composition No. 1 and consisted of a conductive polymer and a non-particulate non-conductive binder polymer, and were densely formed.
  • a light absorber solution A was prepared.
  • the prepared light absorber solution A was applied to the surface of the hole transport layer 13 by a spin coating method (2000 rpm for 60 seconds, and subsequently 3000 rpm for 60 seconds) at room temperature.
  • the applied light absorber solution was dried on a hot plate at 100 ° C. for 40 minutes in a nitrogen atmosphere under normal pressure.
  • a perovskite film (600 nm in thickness) was formed as the photosensitive layer 14 (A) having a perovskite compound.
  • the obtained perovskite compound A (light absorber A) was CH 3 NH 3 PbI 3 .
  • the obtained solution was formed into a film (drying temperature: 40 ° C.) on the photosensitive layer by spin coating (at 3,000 rpm for 90 seconds) to form an electron transport layer 15 having a thickness of 50 nm.
  • Sample No. 101 In the production of the photoelectric conversion element No. 101, the aqueous composition No. 101 was used. Sample No. 1 was replaced by the aqueous composition shown in Table 1. Sample No. 101 was manufactured in the same manner as in the manufacture of the photoelectric conversion element of Sample No. 101. The photoelectric conversion elements 102 to 112 and c1 to c5 were manufactured, respectively.
  • Each hole transport layer of the photoelectric conversion element (Sample Nos. 102 to 112) is composed of a conductive organic material and a non-particulate non-conductive binder polymer contained in each aqueous composition, and is densely packed. Had been formed.
  • Sample No. 113 Manufacture of photoelectric conversion element (sample No. 113)
  • Sample No. 101 was manufactured in the same manner as in the manufacture of the photoelectric conversion element of Sample No. 101.
  • 113 photoelectric conversion elements 10 were manufactured.
  • the hole transport layer of this photoelectric conversion element (Sample No. 113) was made of the aqueous composition No. 13 and consisted of a conductive polymer and a non-particulate non-conductive binder polymer, and were densely formed.
  • the current-voltage characteristics were measured using an IV tester, and the initial photoelectric conversion efficiency was determined.
  • the initial photoelectric conversion efficiency was evaluated based on which of the following evaluation criteria the obtained initial photoelectric conversion efficiency included. In this test, a rating of “C” or higher is a pass level.
  • the moisture resistance of the photoelectric conversion element was evaluated as follows. Each sample No. After storing each of the six photoelectric conversion elements in a constant temperature / humidity chamber at a temperature of 40 ° C. and a humidity of 80% RH for 48 hours, a battery characteristic test was performed in the same manner as in ⁇ Measurement of initial photoelectric conversion efficiency> above. The subsequent photoelectric conversion efficiency was measured. The average value of the photoelectric conversion efficiencies of the six measured samples was determined, and this was used for each sample No. Of the photoelectric conversion element after storage ( ⁇ AFT /%). The humidity resistance and durability of the photoelectric conversion element were evaluated by including the rate of decrease in photoelectric conversion efficiency calculated by the following formula included in any of the following evaluation criteria.
  • Reduction rate (%) 100 ⁇ [100 ⁇ ( ⁇ AFT ) / ( ⁇ INI )] -Evaluation criteria for moisture resistance and durability- A: less than 20% B: 20% or more and less than 30% C: 30% or more and less than 40% D: 40% or more
  • the obtained photoelectric conversion element has an initial Cannot satisfy both the photoelectric conversion efficiency and the moisture resistance and durability. That is, the aqueous composition No. 1 containing only the conductive organic material without containing the particles of the non-conductive binder polymer. When c1 to c3 are used, the aqueous composition No. 1 which does not contain even a non-conductive binder polymer as particles. When c5 is used, none of them exhibit sufficient moisture resistance and durability, and the initial photoelectric conversion efficiency tends to be low.
  • the aqueous composition No. containing no conductive organic material When c4 is used, the initial photoelectric conversion efficiency is inferior. In contrast, when a hole transport layer is formed using an aqueous composition containing a combination of a conductive organic material having a hole transport function and particles of a non-conductive binder polymer, the obtained photoelectric conversion element is obtained. It can be seen that has both initial photoelectric conversion efficiency and moisture resistance and durability. In particular, when the content ratio (mass ratio) between the conductive organic material and the non-conductive binder polymer is in a specific range, the initial photoelectric conversion efficiency and the moisture resistance and durability are well-balanced.
  • the moisture resistance and durability can be significantly improved by using it together with the non-conductive binder polymer particles.
  • a polymer having a structure represented by the formula (S1) defined in the present invention is used as the conductive organic material, the initial photoelectric conversion efficiency and the moisture resistance and durability are both balanced at a high level. From the above results, the photoelectric conversion element and the solar cell of the present invention are excellent in photoelectric conversion efficiency and humidity resistance. Further, the production method of the present invention can produce a photoelectric conversion element and a solar cell exhibiting the above-described excellent characteristics.

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  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

La présente invention concerne un procédé de production d'un élément de conversion photoélectrique qui comprend une couche photosensible, qui contient un composé ayant une structure cristalline pérovskite en tant qu'absorbant de lumière, sur la surface d'une couche de transport de trous. Ce procédé comprend : une étape de formation d'une couche de transport de trous par application et séchage d'une composition aqueuse qui contient un matériau organique conducteur ayant une fonction de transport de trous et des particules d'un polymère liant non conducteur ; et une étape de formation d'une couche photosensible sur la surface de la couche de transport de trous. La présente invention concerne également : un procédé de production d'une cellule solaire par ce procédé de production d'un élément de conversion photoélectrique ; un élément de conversion photoélectrique ; et une cellule solaire.
PCT/JP2019/037470 2018-09-28 2019-09-25 Élément de conversion photoélectrique, cellule solaire, procédé de production d'élément de conversion photoélectrique, et procédé de production de cellule solaire WO2020067097A1 (fr)

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